Precursors, particularly halogenated organoaminosilane precursors that can be used for the deposition of dielectric films, including but not limited to, silicon containing films such as silicon, amorphous silicon, crystalline silicon, microcrystalline silicon, polycrystalline silicon, silicon nitride, silicon oxide, carbon doped silicon oxide, silicon carbo-nitride, and silicon oxynitride films are described herein. In yet another aspect, described herein is the use of the halogenated organoaminosilane precursors for depositing silicon-containing dielectric films in the fabrication of integrated circuit devices. In these or other aspects, the halogenated organoaminosilane precursors may be used for a variety of vapor based deposition processes, including but not limited to, atomic layer deposition (“ALD”), chemical vapor deposition (“CVD”), cyclic chemical vapor deposition (“CCVD”), plasma enhanced chemical vapor deposition (“PECVD”), low pressure chemical vapor deposition (“LPCVD”), and atmospheric pressure chemical vapor deposition (“APCVD”) or liquid based deposition processes, including not but not limited to, spin-on, dip coat, aerosol, ink jet, screen printing or spray deposition or film formation methods.
Several classes of compounds can be used as precursors for silicon-containing films such as, but not limited to, silicon oxide or silicon nitride films. Examples of these compounds suitable for use as precursors include silanes, chlorosilanes, polysilazanes, aminosilanes, and azidosilanes. Inert carrier gas or diluents such as, but not limited, helium, hydrogen, nitrogen, etc., are also used to deliver the precursors to the reaction chamber.
U.S. Pat. No. 6,869,638 describes a CVD method of forming gate dielectric thin films such as gate dielectric, high dielectric constant metal oxides, and ferroelectric metal oxides on a substrate using metalloamide compounds and an aminosilane compounds of the following formula: HxSiAy(NR1R2)4-x-y wherein H is hydrogen; x is from 0 to 3; N is nitrogen; each of R1 and R2 is same or different and is independently selected from the group consisting of H, aryl, perfluoroaryl, C1-C8 alkyl and C1-C8 perfluoroalkyl; and n is from 1-6. Examples of the aminosilane precursors described in the '638 patent include bis(diethylamino)dichlorosilane and tris(diethylamino)chlorosilane.
CWO 2011/123792 describes low temperature, thermal or plasma based ALD methods for forming metal-nitride-containing films from the combination of amino-metal precursors and halogenated metal precursors, preferably forming SiN-containing films from the combination of aminosilane precursors and chlorosilane precursor. The '792 application describes aminosilane precursors comprising an aminochlorosilane having the formula Cl4-xSi(NR′R″)x wherein x=2 or 3, R′ and R″ are independently selected from H or an alkyl group, and R′ and R″ may be linked to form a ring structure and the aminoalkylsilane precursors having the formula R′″4-xSi(NR′R″)x wherein x=1,2, or 3, R′ and R″ are independently selected from H or an alkyl group, R′ and R″ may be linked to form a ring structure and R′″ is an alkyl group having less than 3 carbons.
The reference “Substitution of chlorine in silicon tetrachloride by dimethyl, diethylamino, and piperidino groups”, Breederveld, et al., Research (London) 5:537-9 (1952) describes synthesizing dialkylaminochlorosilanes by the stepwise replace of atoms in SiCl4 with dialkylamino groups to produce one or more of the following compounds: diethylaminotrichlorosilane, di(diethylamino)dichlorosilane, tri(diethylamino)chlorosilane or tetra(diethylamino)silane. A similar procedure was used to prepare piperidinotrichlorosilane and dipiperidinodichlorosilane.
The reference “Molecular structures of some (dimethylamino)halogenosilanes in the gas phase by electron diffraction and the crystal and molecular structures on mono- and di-chloro(dimethylamino)silane by x-ray diffraction at low temperatures”, Anderson et al., J. Chem. Soc., (1987) describes (dimethylamino)halogensilanes SiH2X(NMe2) wherein X═Cl, Br. Or I.
The reference “Chloroaminosilanes. I. Preparation of chloro(dimethylamino)hydrogen silanes”, Washburne et al., Inorg. Nucl. Chem., 5(1):17-19 (1969) describes the preparation of HSiCl2NMe2 (I), HSiCl(NMe2)2 (II), and HSi(NMe2)3 (III) and the related chemical properties of these compounds.
The reference “Preparation of β-cyanoethyltrichlorosilane using silylamine catalysts”, Pike et al., Journal of Organic Chemistry, 27(6): 21-90-92 (1962), describes silylamines of the type (CH3)3SiNR2 which are shown to be directive catalysts by the addition of trichlorosilane to acrylonitrile. An example of a silylamine described in the reference is (iPr2N)SiCl2H.
There is a need in the art to provide precursors that can be used to deposit films comprising silicon that provide one or more of the following advantages: low processing temperatures (e.g., 300° C. or below); relatively good deposition rate; compositional uniformity; and/or high purity.